Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0662—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic containing metal elements
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0698—Compounds of unspecified structure characterised by a substituent only
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/09—Sensitisors or activators, e.g. dyestuffs

Definitions

• a photosensitive material suitable for electrophotography is composed mainly of a free radical former capable of producing freeradical by a radiation energy (F) and an organic photoconductive material (OPl-l) treated with a radiation energy in the presence of an organometallic compound (OM). If desired, a dye base compound or an organic colorization component may be added thereto.
• the photosensitive material may be produced by applying a radiation energy to a formulation containing F OPH and OM.
• This invention relates to a photosensitive material and preparation of said photosensitive material. More particularly, this invention relates to photosensitive material mainly containing an organic photoconductive material and a free radical former capable of producing a free radical by exciting with a radiation energy subjected to a radiation energy in the presence of an organometallic compound and a method of producing said photosensitive material.
• organic photoconductive mate rials there have been known, for example, condensed polynuclear aromatic compounds such as anthracene, pyrene, perylene and the like, heterocyclic compounds such as triphenyl pyrazoline derivatives, acyl hydrazone derivatives and high'polymers such as poly-N- vinylcarbazole. It has been recently contemplated to enhance the photosensitivity of the above mentioned conventional photoconductive materials of low sensitivity by using organic synthetic means. As the result, several useful photoconductive materials have been found. For example, they are brominated poly-N- vinylcarbazole disclosed in Japanese Patent Publication No.
• organic photoconductive materials can be sensitized by a simple sensitizing treatment to give a high sensitivity comparable with or higher than that of conventional selenium or zinc oxide (dye-sensitized).
• free radical former capable of producing free radical when excited by radiation energy, but such photosensitive material or recording material are low in stability. This is due to the free radical former used.
• the free radical former a polyhalogen compound such as carbon tetrabromide is employed, unreacted carbon tetrabromide is essentially present in a photosensitive layer of the photosensitive material or recording material and carbon tetrabromide is so volatile, unstable and poisonous that such photosensitive material or recording material can not be practically used.
• the photosensitive'material according to this invention is composed mainly of a free radical former capable of producing free radical by exciting with a radication energy and an organic photoconductive material irradiated with a radiation energy in the presence of an organometallic compound.
• the photosensitive material' may additionally contain a dye base compound and/or an organic colorization component.
• the above mentioned photosensitive material may be prepared by applying a radiation energy, if desired, together with heat to the composition containing the above mentioned ingredients.
• a photosensitive member may be produced by applying a radiation energy to the above mentioned ingredients present on a support.
• An object of this invention is to provide an electrostatic photosensitive material highly sensitized and method for preparing the same.
• Another object of this invention is to provide a highly sensitive organic photoconductive photosensitive material for electrostatic photography comprising a free radical former capable of producing free radical by' a radiation energy and an organic photoconductive material subjected to a radiation energy in the presence of or'ganometallic compound, and method for production thereof.
• a further object of this invention is to provide an economical and highly sensitive organic photoconductive photosensitive material which is free from complicated organic syntheses and purification step and can be obtained by a simple sensitizing treatment, and method for production thereof.
• Still another object of this invention is to provide a chemically stable and highly sensitive organic photosensitive material and method for production thereof.
• Organic photoconductive materials used in this invention may be selected from the following wide material sources.
• vinylcarbazoles there may be mentioned, for example, vinylcarbazole, poly-9-vinylcarbazole, 9- vinylcarbazole copolymer, 3-nitro-9-vinylcarbazole copolymer, 3-N-methylamino-9-vinylcarbazole copolymer, nitrated poly-9-vinylcarbazole, bromine substituted 9-vinylcarbazole copolymer such as 3-bromo-9- vinylcarbazole copolymer, brominated 9- vinylcarbazole copolymer and 3,6-dibromo-9- vinylcarbazole copolymer, poly-N-vinyl-Elaminocarbazole, bromine substituted poly9- vinylcarbazole such as poly-3-bromo-9-vinylcarbazole, poly-3,6-dibromo-9-vinylcarbazole and brominated-N- vinylcarbazole, iodine substituted poly-9-
• aromatie amino derivatives there may be mentioned, for example, aminopolyphenyl, allylideneazine, N,N'-diallyl-N,N'-dibenzyl phenylenediamine, N,N,N- ',l ⁇ l-tetrabenzyl-p-phenylenediamine, N,N-diphenylp-phenylenediamine, N,N-dinaphthyl-pphenylenediamine, and 4,4-bisdimethylaminobenzophenone.
• diphenylmethanes and triphenylmethanes there may be mentioned, for example, diphenylmethane dye leuco base and triphenylmethane dye leuco base.
• D As compounds having heterocyclic ring, there may be mentioned, for example, oxadiazole, aminothiazole, 4,l,2-triazole, imidazolone, oxazole, imidazole, pyrazoline, imidazolidine, polyphenylene thiazole, 1,6-methoxyphenazine, and pyrazolinopyrazoline derivatives.
• benzthiazole benzimidazole
• benzoxazole derivatives such as 2-(4-diamino phenyl)-benzoxazole, 2-(4'-dimethylaminophenyl)- benzoxazole, aminoacridine, quinoxaline, diphenylene hydrazone compound, pyrrocoline derivatives and 9,l0-dihydroanthracene derivatives.
• triphenyl-pentl -ene-4-yn-3-o'l triphenyl-pentl -ene-4-yn-3-o'l.
• condensation products there may be mentioned,
• a five ring compound there may be mentioned p-bis(2-phenyl-4-thiazolyl) benzene; as a Q- thiazolyl seven ring compound, 2,4-bis[4-(2-phenyl-4- thiazolyl)-phenyl] thiazole; as a nine ring compound, l,4-bis[4- ⁇ 4-(2-phenyl-4-thiazolyl)-phenyl ⁇ thiazolyl]- benzene.
• a free radical former employed in this invention is a material capable of producing a free radical by excitation with a radiation energy.
• a free radical former can be selected from the following classes of widely ranged substances.
• polyhalogen containing compounds there may be used a compound of the general formula:
• R represents hydrogen, alkyl, halogen atom selected from Cl, Br and l, I
• R represents substituted or unsubstituted alkyl, aryl or heterocyclic group
• X, Y and Z are similar or dissimilar, and hydrogen, alkyl or halogen atom selected from Cl, Br and I, at least one of X, Y and Z is halogen atom, for example, CBr C1 CHl C Cl csrcl CCl,, CHBr CHCl C BR C HBr C H CBr ClBr ClCl Cl-llCl CHlBr CBrCl CHBrCl 2,2,2-trichlorotoluene, 2,2,2-tribromo acetophenone, l,l l -tribromo-2-methyl-2-propanole, l,l,2,2-tetra bromoethane, 2,2,2-tribromoethanole, CH CI Cl-l Br CH I ClCH CH Cl, BrCH CH Br, Ci-I Cl-lCl CH CHBr CHCI CHCI ClCH
• vicinal polyketaldonyl compounds for example, vicinal polyketaldonyl compounds, a-carbonyl alcohols, acryloin ethers, zit-hydrocarbonsubstituted acryloins, polynuclear quinones.
• captane thiole, metalmercaptide, dithiocarbamates, O-alkylxanthene esters, and thiuram derivatives.
• peroxide compound there may be for example, hydroperoxide, dialkylperoxide, diacrylperoxide and diaroylperoxide.
• azo and diazo compounds there may be mentioned, for example, azonitrile compound, diazo compound such as p-nitrobenzene diazonium-pchlorobenzene sulfonate.
• a compound giving an especially excellent result is a polyhalogen containing compound.
• the representative organometallic compounds used in this invention are alkylmetallic compound, arylmetallic compound, alkylarylmetallic compound and cyclopentadienyl-metallic compound.
• Metals in alkymetallic compound, arylmetallic compound and alkylavrylmetallic compound are metal elements in the Groups [VB and VB of the Periodic Table.
• the metals are preferably Ge, Sn, Pb, P, As, Sb and Bi.
• the metal in cyclopentadienyl compound is transition metal elements in the Groups IIIA, IVA, VA, VIA, VIIA and VIIIA.
• the transition metal elements as the Group IIIA element are Sc, Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er and Yb; as the Group IVA element Ti, Zr and Hf; as the Group VA element V, Nd and Ta; as the Group VIA element Cr, Mo, W and U; as the Group VIIA element Mn, Tc and Re; and as the Group VIIIA element Fe, Co, Ni and Ru.
• alkylmetallic compound arylmetallic compound and alkylarylmetallic compound
• triphenylmetallic compound such as triphenyl bismuthine, triphenylstibine, triphenylarsine and triphenylphosphine
• tetraphenylmetallic compound such as tetraphenyldistibine, tetraphenyllead, tetraphenyltin, tetraphenylarsine and tetraphenylgermanium
• benzyltriphenyllead trimethyltriphenylditin, hexamethylditin and hexaphenylditin.
• the alkyl group, aryl group or alkylaryl group is attached to the metal element so as to satisfy the valency of the metal element to form a metal carbon bond.
• organometallic compounds having the Group IIIA element there may be mentioned, for example, cyclopentadienyl compounds of scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, dysprosium, erbium and ytterbium.
• organometallic compound having the Group IVA transition elements there may be mentioned, for example, bis (cyclopentadienyl) titanium, dihalogenated bis(cyclopentadienyl) titanium, bis (cyclopentadienyl) titanium diaryl, and bis (cyclopentadienyl) zirconium dibromide.
• an organometallic compound having the Group VA transition element there may be mentioned, for example, bis (cyclopentadienyl) vanadium dihalide, bis (cyclopentadienyl) niobium tribromide, bis (cyclopentadienyl) tantalum tribromide, bis (cyclopentadienyl) vanadium, and cyclopentadienyl vanadium tetracarbonyl.
• organometallic compound having the Group VIA transition element there may be mentioned, for example, bis (cyclopentadienyl) chromium, bis (cyclopentadienyl)- p, -pentacarbomonooxide bimolybdenum, bis (cyclopentadienyl)- p. -hexacarbonmonooxide-bitungsten, tris (cyclopentadienyl) uranium chloride.
• VIIA transition element there may be mentioned, for example, bis (cyclopentadienyl) manganese, and hy drogenated bis (cyclopentadienyl) rhenium.
• an organometallic compound having the Group VIIIA transition element there may be mentioned, for example, bis (cyclopentadienyl) iron [ferrocene], bis (cyclopentadienyl) iron dicarbonyl, cyclopentadienyliron dicarbonyl chloride, cyclopentadienylirondicarbonyl cyanate, bis (cyclopentadienyl) cobalt bromide, bis (cyclopentadienyl) cobalt [cobaltocene], cyclopentadienyl cobalt dicarbonyl, bis (cyclopentadienyl) nickel [nickelocene], cyclopentadienylnickelnitrosyl, bis (cyclopentadienyl) ruthenium and bis (cyclopentadienyl) ruthenate.
• bis (cyclopentadienyl) iron [ferrocene] bis (cyclopentadienyl) iron dicarbonyl,
• organometallic compounds may be used.
• organometallic compounds there are preferably used triphenylbismuthine, triphenylphosphine, tetraphenylarsine, ferrocene and cobaltocene.
• the radiation energy source used in this invention is selected depending upon organometallic compounds, free radical formers, organic photoconductive materials and/or solvent used. Any kind of light source may be used as far as it can produce free radical from a free radical former in the sensitization system.
• a light source emitting a large amount of ultraviolet ray or near ultraviolet ray such as mercury (low pressure, high pressure or super high pressure), metal halide lamp and xenon lamp is used.
• a radiation energy such as ultraviolet ray can be applied together with heat to accelerate the decomposition of free radical formers by selecting the temperature at which the radiation energy is applied and the time of irradiation in such a manner that there are balanced the degree of sensitization and undesirable secondary effects such as remarkable colorization and gellation.
• the effective wave length of radiation energy is, for example, illustrated below.
• Azo compound-340- 400 my. Among them, effective wavelength for some halogen compounds is shown below.
• the sensitization treatment may be effected as follows. An organic photoconductive material, a free radical former and an organometallic compound are brought into coexistence to form a uniform solution by using an appropriate solvent and a radiation energy is applied to the resulting solution for sensitization treatment. In this case, if an organometallic compound is not used, it is very difficult to select an appropriate solvent since the solvent should have a sufficient solubility to the organic photoconductive material and the free radical former, and furthermore such a solvent which reduces the sensitization effect should be avoided.
• benzene and monochlorobenzene can enhance the sensitization effect while tet- 'rahydrofuran anddioxane reduce the sensitization effeet.
• the present inventors have found that the reduction of sensitization effect caused by solvent is remarkably weakened by incorporating a small amount of an organometallic compound in the reaction system.
• an organometallic compound for example, there may be used methylene chloride, chloroform, toluene and xylene which are usually not preferable, and further tetrahydrofuran and dioxane which are extremely unfavorable can also be sufficiently used.
• the selection range of solvent is very broadened.
• organometallic compound results in high sensitivity.
• the sensitizing effect of the organometallic compounds is illustrated in the Examples appearing later.
• a solution containing a free radical former and an organic photoconductive material has a color or the solution contains additionally a dye base compound or an organic colorization component, the sensitization effect can be visually observed since the coloriz ation of the solution is markedly accelerated.
• the sensitization treatment may be carried out by various methods such as, for example, applying a radiation energy to a solution comprising an organometallic compound and a free radical former followed by mixing with a solution of an organic photoconductive solution, or applying a radiation energy to each of a solution containing a free radical former and an organic photoconductive material and a solution containing a free radical former and an organometallic compound followed by mixing these two solutions, or applying a radiation energy to a solution containing an organic photoconductive material, a free radical former and an organometallic compound coated on a base support.
• a photosensitive material of higher sensitivity can be obtained by additionally incorporating a dye base compound or organic colorization component thereto.
• any solvent can be selected as far as the solvent can dissolve the organic photoconductive material. This free selection of solvent is very valuable.
• the free radical former is a polyhalogen compound of the formula where R is hydrogen, halogen, alkyl or aryl (substituted or unsubstituted) and each X may be, the same or differenflchlorine, bromine or iodine, when thepolyhalo gen compound is exposed to a sufficient amount of radiation energy, the following reaction proceeds;
• the reactions shown in Formulas (l) and (2) can be effectively caused and the reaction time is shortened by the action of the organometallic compound and simultaneously the reaction conditions such as selectivity of solvent, tolerable amounts of impurity, and temperature range for reactions of Formulas (l) and (2) can be broadened. And further the addition of organometallic compound results in improvement in photosensitivity.
• the abovementioned organometallic compound and halogen compound are added to a solution of organic photo conductive material and the resulting solution is subjected to a radiation energy sufficient to cause the reactions in Formulas (1) and (2) to sensitize remarkably the organic photoconductive material.
• the amount of the free radical former used in this invention is appropriately'selected depending upon each particular photoconductive material and amount of radiation energy. In general, the amount of the free radical former is preferably l 30 percent by weight.
• the amount of organometallic compound used in this invention is appropriately selected depending upon each particular photoconductive material, free radical former, and amount of radiation energy. In general, the amount of the organometallic compound preferably ranges from IO' to l0 percent by weight.
• binder resins are polystyrene resin, polyvinyl chloride resin, phenolic resin, polyvinyl acetate resin, polyvinyl acetal resin, epoxy resin, xylene resin, alkyd resin, polycarbonate resin and acrylonitrile-styrene resin.
• plasticizers are dioctylphthalate, tricresylphosphate, diphenyl chloride, methyl naphthalene, p-terphenyl and diphenyl.
• a dye sensitizer or Lwiss acid usually used in electrophotography singly or in combination. Furthermore, it is also effective for increasing photosensitivity of the photosensitive material to add a dye base compound capable of forming a coloring matter by the reaction with a free radical former caused by a radiation energy. In addition, it is effective to add an organic colorization component capable of forming a coloring material by the reaction with a free radical former caused by a radiation energy.
• leuco base or carbinol base there may be mentioned, for example, leuco base of triphenylmethane dye such as leuco malachite green,'leuco crystal violet, leuco methylviolet, leuco opal blue; carbinol base of triphenylmethane dye such as carbinol crystalviolet, carbinol methylviolet; leuco base or carbinol base of diphenylmethane dye having the formula where R,, R R and R represents a member selected from the group consisting of hydrogen, alkyl, aralkyl and aryl (substituted or unsubstituted), when X is l-l,
• R represents a member selected from the group consisting of hydrogen, alkyl, aryl and aralkyl (substituted or unsubstituted), R represents a member selected from the group consisting of phenyl, a-naphthyl and B-naphthyl; R represents a member selected from the group consisting of alkyl, aryl and aralkyl (substituted or unsubstituted), such as diphenylamino, N-methylaniline, N,N-dimethylaniline, N-ethylaniline, N,N-diethylaniline, phenyl-a-naphthylamine, phenylwherein R represents a member selected from the B-naphthylamine, triphenylamine methylidiphenylamine.
• Carbazoles have the general formula:
• R represents a member selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl and aryl (substituted or unsubstituted), R and R are similar or dissimilar, a member selected from the group consisting of hydrogen, alkyl,alkenyl, aralkyl, alkoxy, halogen and dialkylamino.
• each of R5 is similar or dissimilar, a member selected from the group consisting of hydrogen, alkyl, alkoxy, halogen and dialkylamino.
• indole 2-methylindole, 1,2-dimethylindole,
• 1,3,4-oxathiazoles there may be mentioned, for example,- 2-,5-bis-[4'-dimethylaminophenyl-1'1- l,3,4-oxadiazole, 2,5-bis-[4'-diethylaminophenyl-l 1,3,4-oxadiazole, 2,5-bis-[4'-n-propylaminophenyl- 1' ]-l ,3,4-oxadiazole and 2,5-bis-[4 cyclohexylaminophenyl-l l ,3,4-oxadiazole.
• 1,3,4-triazoles there may be mentioned, for example, l-methyl-2,5 bis-[4'-N,N-diethylaminophenyl- 1 1,3,4-triazole, 2,5-.bis-[4'-N,N-diethylaminophenyl-l ']-l ,3,4-triazole, 2,5-bis-[4' aminophenyl-l 1,3,4-triazole and 2,5 -bis-[4'-N-ethylaminophenyl-l '1- 1 ,3 ,4-triazole.
• imidazoles there may be mentioned, for example, 4-(4'-dimethylaminophenyl)-5-(4"-chlorphenyl)- imidazole, l-methyl-2-(diethylaminophenyl)4 ,5- diphenyl-imidazole, 4-(4'-dimethylaminophenyl)-5- phenyl-imidazole and 2-(4-dimethylaminophenyl)- 4,5-diphenyl-imidazole.
• pyrazolines there may be mentioned, for example, 1,3 ,S-triphenylpyrazoline, 1,5-diphenyl-3- styryl-pyrazoline, l,3-diphenyl-5-p-oxyphenylpyrazoline, and 1-phenyl-3-p-dimethylaminostyryl-5-pdimethylaminophenyl-pyrazoline.
• aminophenyl substituted oxazoles there may be mentioned, for example, 2-(4'- J.
• 1,3-diphenyl-tetrahydroimidazoles there may 7 be mentioned, for example, l,3-diphenyl-2-(4- dimethylaminophenyl)-tetrahydroimidazole, 1,3- diphenyl-2-styryl-tetrahydroimidazole and l ,3-
• phenazinecompounds there may be mentioned, for example, 1,6-dimethoxyphenazine, and 1,6- dimethylphenazine.
• acridine compounds there may be mentioned, for example, 3,6-bis(diamino)acridine, 3,6-bis(dimethylamino)-acridine and acridine.
• acylhydrazone derivatives there may be mentioned, for example, compounds having'the formulae and ' and R.
• spiropyrans there may be mentioned, for example, l,3,3-trimethylindolinobenzopyrylspiran, 1,3,3-trimethylind'olino-6'-nitrobenzopyrylspiran, 1,3,3-trimethylindolino-6'-nitro-8-methoxybenzopyrylspiran and l,3,3-trimethylindolino-6-methoxy-B nitrobenaopyrylspiran.
• a photosensitive material may be prepared by applying a radiation energy simultaneously with heat to a free radical former capable of producing free radical by a radiation energy and an organic photoconduc tive material in the presence of an organometallic compound; or applying a radiation energy to a solution system containing a free radical former capable of producing free radical by a radiation energy, an organic photoconductive material and an organometallic compound; or applying a radia tion energy to a solution system containing a free radical former'capable of producing free radical by a radiation energy and an organometallic compound and mixing the solution system thus treated with a solution system containing at least an organic photoconductive material; or mixing asolution system containing a free radicalformer capable of producing free radical by a radiation energy, an organic photoconductive material 'and an organometallic compound irradiated by a radiation energy with a solution system containing a free radical former and, if desired, additionally an organometallic compound irradiated by a radiation energy.
• a dye base compound and/or an organic colorization components may be added to the system.
• a solution containing an organic photocon'ductive material, a free radical former and an organometallic compound subjected to or to be subjected to a sensitizing treatment by using a radiation energy may be applied to a transparent or opaque support by conventional coating methods such as roll coating method, wire-bar coating method, air-knife method and the like.
• the radiation energy may be applied to the solution beforeor after the solution is coated on a support.
• a radiation energy is applied to the solution coating while the coating is being continuously formed followedby drying.
• a dye base compound or an organic colorization component may be added at this stage.
• the method of producing a photosensitive member according to this invention is simple and of high efficiency.
• the thickness of the resulting photoconductive layer on the support may be adjusted to a range of from several microns to several tens microns. For usual purposes, it is less than microns and several microns.
• metal sheet such as aluminum, copper, zinc and silver
• any support hav ing a surface resistivity lower than that of the photoconductive layer may be used.
• such material having a resistivity of lower than 10 0,, preferably lower than 10 0 may be used.
• exposing, developing and fixing steps For example, positive charge is accumulated and its potential reaches 150-600 V. by passing the photosensitive member below the corona discharger charged with +6 KV in the dark several times. Then, from an appropriate light source such as a tungsten lamp, light is projected through an adequate positive pattern, then the electric charge at the exposed region is neutralized. Then, the latent image thus formed'is developed with a negatively charged toner by, for example, a magnet brush developing method, cascade developing method or a furbrush developing method to produce the positive image. This image may be fixed by heating or passing it through an appropriate solvent vapor. Liquid developing method may also be used.
• the liquid developer as necessary constituents a coloring component and a carrier liquid, it is possible to add to it a controlling agent and an agent improving fixing property when desired.
• the electric charge applied by corona charging may be a positive charge or a negative charge.
• the required exposure amount was about 250 lux.sec.
• the resulting photosensitive paper When the solution containing the above-mentioned ingredients was coated on the above-mentioned base paper and irradiated with a high pressure mercury lamp of 100 watt at a distance of 150 mm for 5 seconds, the resulting photosensitive paper also gave a positive image of high fidelity to the original image under the reproduction conditions similar to the above ones while 30 seconds irradiation was necessary to give the same photosensitivity when the solution excluding triphenylbismutin was employed.
• the sensitization effect by triphenylbismutin was able to be measured by the degree of colorization of the soltuion caused by the light irradiation. That is, when triphenylbismutin is present, the solution was colorized to bluish by the light irradiation for, 5 minutes while it took 15 minutes to colorize to bluish in the absence of triphenylbismutin.
• a mixture of the above-metnioned ingredients was used to produce a photosensitive paper in a way similar to Example l, the light irradiation being effected for 5 minutes.
• the resulting photosensitive paper was given a uniform negative charge of about 380 V by corona charging by using a charging apparatus of about 5.5 KV, contacted with an original positive film, exposed to a 150 watt tungsten lamp at 200 lux.sec., and soaked in a positive liquid developer to produce clear positive images of high fidelity to the original image.
• EXAMPLE 3 Poly-9-vinylcarbazole (Luvican M-l70, trade name, supplied by BASF) a g. Carbon tetrabromide 400 mg. Bis (cyclopentadienyl) titanium diphenyl 8 mg. Benzene 200 ml.
• Example 2 The mixture of the above-mentioned ingredients was irradiated in a manner similar to Example 1. Then, 5 ml. of a solution of 80 mg. of l, 3, S-trinitrobenzene in benzene was added thereto as Lewis acid. Then, following the procedure of Example 1, there was produced a photosensitive paper.
• the resulting photosensitive paper was given a uniform negative charge of about 350 V by corona charging using a charging device of about 5.5 KV, contacted with an original positive film, exposed to a lSO watt tungsten lamp at 120 lux.sec., and soaked in a positive liquid developer to form clear positive images of high fidelity to the original positive EXAMPLE 4
• Poly-9 -vinylcarbazole (PO-098, trade name, supplied by 'A solution composed of the above ingredients was coated on a base paper of 79 g/m, which was treated with a hydrophilic'polymer so as to inhibit the permeation of a solvent, in an amount of about 5 g/m by a double roll coating method and, after coating is finished, the resulting coating was immediately irradiated by a 500 watt xenon lamp at a distance of about 1 0 cm for 5 seconds to produce a photosensitive paper.
• the resulting photosensitive paper was given a uniform negative charge of about 280 V by corona charging by using a charging device of about 5.5 KV, placed under an original positive film, exposed to a.15 watt tungsten lamp at 150 lux.sec., and soaked in a positive liquid developer to produce a positive image of high fidelity to the original image.
• Example 1 a solution obtained by mixing the listed ingredients is irradiated with a watt high pressure mercury lamp for 5 minutes, coated on a base paper, and dried to produce a photosensitive paper.
• the resulting photosensitive paper is subjected to corona charging by a charging device of about 5.5 KV, contacted with an original positive film and exposed to a watt tungsten lamp.
• Examples 5 39 there are shown a formulation for the solution, an exposure amount, necessary for obtaining clear positive images and, for comparison, an exposure amount necessary for obtaining clear positive images when the organometallic compound is The exposure amount needed 170 lux.sec. When triphenylphosphine was not contained, the exposure amount was 350 lux.sec.
• the exposure amount needed 9 0 lux.sec. However, when triphenylbismuthine was not contained, the exposure amount was 300 lux.sec.
• EXAMPLE 8 Poly-3-bromo-9-vinylcarbazole 8 g. Tribrornornethylphenylsulfone 400 mg. 2-[ I, 3-Dioxo-hydrinedenyl42)] quinoline 50 mg. Cobaltocene 0.5 mg. Monochlorbenzene 200 ml. Methyl violet 20 mg.
• the exposure amount needed 80 lux.sec. When cobaltcene was not contained, the exposure amount was 280 lux.sec.
• EXAMPLE 9 Graft-copolymer of 9-vinylcarbazole and ethylacrylate 8 g. Bromoform 400 mg. Leuco methylviolet 80 mg. Cobaltcene 0.5 mg. Toluene 200 ml. Diphenyl chloride 2 g. 2, 4, 7-Trinitro-9-fluorenone 50 mg.
• the exposure amount needed 95 lux.sec. When tri phenylbismuthine was not contained, the exposure amount was 280 lux.sec.
• EXAMPLE 1 Poly-9-vinylcarbazole (trade name Luvican M-l70 supplied by BASF) 8 g. Carbon tetrabromide 400 mg. 4- (Edimethylaminostyryl) quinoline 80 mg. Tetraphcnyllead 8 mg. Benzene 200 ml.
• the exposure amount needed 90 lux.sec. When tetraphenyllead was not contained, the exposure amount was 255 lux.sec.
• EXAMPLE l2 Graftcopolymer of 9-vinylcarbazole and ethylacrylate (in the ratio of 9o 10) 8 g Carbon tetrabromide 200 mg. N-vinylcarbazole 800 mg. Bis (cyclopentadienyl) zirconium dibromide 8mg. Benzene 200 ml. Diphenyl chloride 2 g. 2, 4, 7-trinitro-9-fluorenone 50 mg.
• the exposure amount needed l85 lux.sec. When his (cyclopentadienyl) zirconium dibromide was' not contained, the exposure amount was 395 lux.sec.
• EXAMPLE 14 Bis- 4, 4-dialkylaminobenzylideneazine Copolymer of acrylonitrile and styrene (trade name Estylene AS-61NT supplied by Yahata Kagaku') 4 g. Pentabromodimethylsulfoxide 1 400 mg. 4-[2-(3-ethyl-2(3H)- benzothiazolylideneamino) vinyl] quinoline 80 mg. Ferrocene 0.1 mg. Methylene chloride 200 ml. Acridine yellow 20 mg. Chloranil 70 mg.
• EXAMPLE 15 Nitrated poly9vinylcarbazole (having 0.06 molars of nitro radical per one carbazole unit mainly at 3-position of carbazole ring) 8 g. lodoform 100 mg. 2.5-Bis- [4'-dimethylaminophenyl-l -l. 3, 4-oxadiazole l00 mg. Triphenylarsine 8 mg. Benzene 200 ml.
• the exposure amount needed 275 lux.sec. When triphenylarsine was not contained, the exposure amount was 560 lux.sec.
• the exposure amount needed 155 lux.sec. When triphenylphosphine was not contained, the exposure amount was 335 lux.sec.
• the exposure amount needed lux.sec. When nickelocene was not contained, the exposure amount was 210 lux.sec.
• the exposure amount needed 830 lux.sec. When bis (cyclopentadienyl) niobium tribromide was not contained, the exposure amount was 1540 lux.sec.
• EXAMPLE 19 Poly-9-vinylcarbazole (trade name Luvican M-l70 supplied by BASF) 8 lodoform 400 mg. Triphenylbismuthine 4 mg. 2, 4, 7-Trinitro-9-fluorenone 50 mg. Benzene 200 ml.
• the exposure amount needed 55 lux.sec. When triphenylbismuthine was not contained, the exposure amount was lux.sec.
• EXAMPLE 2O N,N,N,N'-tetrabenzylP-phenylendiamine
• Polyvinylbutylal resin (trade name S-lec ELS supplied by Sekisui Kagaku) Hexabromodimethylsulfoxide 3-Ethyl-5- l3-ethyl-2(3H)- benzothiazolylidene] rhodanine Bis (cyclopentadienyl) chromium 4 mg. Toluene 4 g. 400 mg.
• EXAMPLE 21 Bis-4,4-dialkylaminobenzylideneazine 4 g. Copolymerization resin of acrylonitrile and styrene (trade name Estylene AS-GINT supplied by Yahata Kagaku) 4 g. Di-tertiallybutylperoxide 400 mg. 4-(4'-dimethylaminophenyl)- 5-(4"-chlorphenyl) imidazole 80 mg. Bis (cyclopentadienyl) tantalum tribromide 16 mg. Methylene chloride 200 ml.
• EXAMPLE 22 Nitrated poly-9-vinylcarbazole (having 0.06 mole of nitro radical per one carbazole unit mainly at 3-position of carbazole ring) 8 g. Bromoform 400 mg. Triphenylbismuthine 16 mg. Benzene The exposure amount needed TIC-lux.sec. When triphenylbismuthine was not contained, the exposure amount was 530 lux.sec. 4
• Epoxy resin (trade name Epikote 1004 supplied by ShellOil) 4 g.
• the exposure amount needed 2060 lux.sec. When bis ('cyclopentadienyl) vanadium was not contained, the exposure amount was 3750 lux.sec.
• EXAMPLE 24 Bis-4,4-diallylaminobenzylideneazine 4 g. Modified phenolic resin (Beckacite H00, trade name. supplied by Japan Reichhold Chemical Co.) 4 g. Tribromomethylphenylsulfone 400 mg. 1,3,5-Triphenylpyrazoline 80 mg. Tetraphenyl tin 16 mg. Chlorobenzene 200 ml.
• Modified phenolic resin (Beckacite H00, trade name. supplied by Japan Reichhold Chemical Co.) 4 g. Tribromomethylphenylsulfone 400 mg. 1,3,5-Triphenylpyrazoline 80 mg. Tetraphenyl tin 16 mg. Chlorobenzene 200 ml.
• Polycarbonate resin (Panlite C, trade name,
• the exposure amount needed 440 lux.sec. In the absence of tetraphenyl lead the exposure amount was 1280 lux.sec.
• EXAMPLE 26 Leuco malachite green 4 g. Polystyrene resin (Piccolastic D-l00, trade name, supplied by ESSO) 4 g. Diphenylthiocarbazone 400 mg. Z-(P-Dimethylarninostyryl) quinoline lSO mg. Bis (cyclopentadienyl)-P-pentacarbonmonooxide-bimolybdenum 4 mg. Benzene 100 ml. Methylene chloride l00 ml.
• the exposure amount needed 2300 lux.sec. In the absence of his (cyclopentadienyl)-P-pentacarbonmonooxide-bimolybdenum, the exposure amount was 4150 lux.sec.
• EXAMPLE 28 4,4-Bis-dimethylamino-benzophenone 4 g. Polycarbonate resin (lupilon E, trade name, supplied by Mitsubishi Edogawa Kagaku) 4 g. Carbon tetrabromide 400 mg. Triphenylbismutin 4 mg. Methylene chloride 200 ml.
• the exposure amount needed 100 lux.sec. In the absence of triphenylbismutin, the exposure amount was sence of nickelocene, the exposure amount was 4930 lux.sec.
• EXAMPLE 30 Leuco crystal violet 4 Epoxy resin (Epikote 1004, trade name, supplied by Shell Petroleum Co.) 4 g. Hexabromodimethylsulfoxide 400 mg. 0 tolydine I00 mg.
• the exposure amount needed 520 lux.sec. In the absence of bis (cyclopentadienyl) iron dicarbonyl, the exposure amount was 950 lux.sec.
• EXAMPLE 33 phenylenediamine 4 g. Modified phenolic resin (Beckacite 1100, trade name,
• EXAMPLE 34 Bis-4,4-diallylaminobenzylidene azine 4 g. Modified phenolic resin (Beckacite 1.100, trade name, supplied by .lapan'Reichhold Chemical Co.) 4 g. Tribromomethylphenylsulfone 400 mg. Hexaphenylditin 4 mg. Chlorobenzene 200 ml.
• Modified phenolic resin (Beckacite 1.100, trade name, supplied by .lapan'Reichhold Chemical Co.) 4 g. Tribromomethylphenylsulfone 400 mg. Hexaphenylditin 4 mg. Chlorobenzene 200 ml.
• EXAMPLE 36 Leuco crystal violet 4 g. Acrylonitrile-styrcne copolymer (E stylene AS-GINT, trade name,
• the exposure amount needed 600 lux.sec. In the absence of ferrocene, thev exposure amount was 2300 lux.sec.
• EXAMPLE 37 Leuco crystal violet 4 g. Acrylonitrile-styrene copolymer (Estylene AS-6lNT, trade name,
• the exposure amount needed 780 lux.sec. In the absence of tetraphenylgermanium, the exposure amount was 1450 lux.sec.
• a solution composed of the above ingredients was placed in a 50 ml. quartz Erlenmeyer flask, and irridated by a high pressure mercury lamp of 100 watt at adi stance of 10 cm for about 20 minutes. (When triphenyl phosphine was not contained, the solution was irradiated for 30 minutes.)
• the resulting photosensitive paper was given a uniform negative charge of about 350 V by corona charging by using a charging device of about 5.5 KV, contacted with an original positive film, to a 150 watt tungsten lamp at 150 lux.sec. and soaked in a positive liquid developer to form positive images of high fidelity to the original image.
• a solution composed of the above ingredients was placed in a 50 ml. quartz Erlenmeyer flask, irradiated with a 500 watt xenon lamp at a distance of 10 cm for about 5 minutes. When triphenylbismutin was not used, 30 minute irridiation was necessary.
• a solution composed of the above ingredients was placed in a 50 ml. quartz Erlenmeyer flask, and irradiated by a 500 watt xenon lamp at a distance of 20 cm for about 10 minutes. When triphenylbismutin was not used, 30 minute irradiation was necessary.
• a solution of (I) and a solution of (II) were irradiated by a l00 watt high pressure mercury lamp at a distance of about 10 cm for about 5 minutes. (When triphenyl bismutin was not used, the irradiation time was 10 minutes.) Then, these two solutions were immediately mixed, allowed to stand at a dark place for l0 hours, coated on a polyester film ,1. thick) having an aluminum deposit to form a coating of about 5 p. thick and dried naturally to produce a photosensitive film.
• the photosensitive film thus obtained was subjected to an electrophotographic process similar to Example 40, and an exposure amount of 120 lux.sec. was required to produce positive images of high fidelity to the original image.
• a solution composed of the above ingredients was coated on a base paper of 60 g/m (the surface on which the solution is applied was treated with a hydrophilic polymer so as to inhibit the permeation of a solvent) in an amount of about 6 g/m by a kiss roll coating method and then immediately irradiated by a high pressure mercury lamp (100 watt) at a distance of about 15 cm for 10 seconds.
• a high pressure mercury lamp 100 watt
• the required irradiation time was 30 seconds.
• the coating was dried by hot air at 70C at a wind velocity of m/sec. to produce a photosensitive paper.
• the resulting photosensitive paper was subjected to an electrophotographic process similar to Example 44 and the required exposure amount forproducing a positive image of high fidelity to the original image was 115 lux.sec.
• a sensitized electrographic photosensitive memher which comprises a support having coated thereon a layer of photoconductive photosensitive material, said layer comprising an organic photoconductive material, a free radical former capable of producing free radicals for sensitizing said organic photoconductive material when excited by radiation energy having ultraviolet radiation and an organometallic compound incapable of liberating free radicals under the exposure used to sensitize said layer but capable of catalyzing the sensitizing ability of the radical former, said support having been exposed to said radiation energy to sensitize said layer.
• a photosensitivematerial according to claim 1 in which a sensitizing material is incorporated in a mixture of a free radical former and an organic photoconductive material reactively treated by a radiation energy.
• a photosensitive member according to claim 1 wherein at least one organometallic compound is selected from the group consisting of triphenylbismuthine, triphenylphosphine, tetraphenylarsine, ferrocene and cobalto'cene.
• a photosensitive member according to claim 1 including at least one organic photosensitive material selected from the group consisting of vinyl carbazoles, aromatic amine derivatives, diphenylmethane compounds and 'triphenylmethane compounds.
• the vinyl carbazole is at least one member selected from the group consisting of poly-9- vinylcarbazole, bromine substituted poly-9- vinylcarbazole and iodine substituted poly-9- vinylcarbazole.
• a photosensitive member according to claim 1 including at least one free radical former selected from the group consisting of polyhalogen containing compound, carbonyl'compound, organic sulfur compound, peroxide, azo compound, and diazo compound.
• a photosensitive material according to claim 23 in which the poly-halogen containing compound is a compound of the formula where R is selected from the group consisting of hydrogen, al k yl, chlorine, bromine, iodine,
• R is selected from the group consisting of substituted or unsubstituted alkyl, aryl and hetrocyclic residue
• X, Y and Z are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, Cl, Br and I and at least one of X, Y and Z is halogen atom.
• a photosensitive member according to claim 1 including a colorization component selected from the group consisting of a dye base or an organic colorization component capable of forming a coloring material by reaction with said free radical former upon radiation excitation.
• R is a member selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl and aryl (substituted or unsubstituted) and R and R are, similar or dissimilar, selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl, alkoxy, halogen, and dialkylamino.
• R is a member selected from the group consisting of hydrogen, alkyl aralkyl and aryl (substituted or unsubstituted an each R is, similar or dissimilar, selected from the group consisting of hydrogen, alkyl,

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• 1971
  • 1971-02-01 US US00111626A patent/US3765883A/en not_active Expired - Lifetime
  • 1971-02-03 BE BE762466A patent/BE762466A/xx unknown
  • 1971-02-04 DE DE2105199A patent/DE2105199C3/de not_active Expired

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